3,8-双乙酰基次卟啉二甲酯的合成

以氯化血红素(Ⅰ)为原料，经过溴化氢-冰醋酸加成反应、羟基亲核取代反应和无水氯化氢催化酯化反应制得3,8-双-(1-羟基乙基)次卟啉二甲酯(Ⅲ)，然后通过琼斯试剂氧化反应制备了3,8-双乙酰基次卟啉二甲酯(Ⅳ)。 考察了血红素与溴化氢-冰醋酸饱和溶液反应过程中温度和时间对3,8-双-(1-羟基乙基)次卟啉二甲酯(Ⅲ)产率的影响；改进了酯化反应的实验条件；选用了廉价易得、选择性较好的羟基选择性氧化剂。 实验结果表明，当反应温度为35 ℃、反应时间为25 h时，血卟啉(Ⅱ)的产率最高，为98.5%；当催化剂为无水氯化氢时产物(Ⅲ)的产率最高，为72.1%；使用琼斯试剂做氧化剂使实验成本大大降低。 通过1H NMR、MS和IR测试技术对产物结构进行了表征。

Synthesis of 3,8-Bisacetyl Deuteroporphyrin Dimethyl Ester

3,8-Bis-(1-hydroxyethyl)deuteroporphyrin dimethyl ester(Ⅲ) was prepared from hemin(I) by the ways of HBr-H3CCOOH addition reaction, OH- nucleophilic substitution reaction and anhydrous hydrogen chloride catalyzed esterification. It was then oxidized by Jones reagent to form 3,8-bisacetyl deuteroporphyrin dimethyl ester(Ⅳ). The effects of reaction temperature and reaction time on the yield of 3,8-bis-(1-hydroxy-ethyl) deuteroporphyrin dimethyl ester(Ⅱ) were studied. The conditions of esterification reaction were modified. A cheaper and selective oxidant was used in the synthesization of 3,8-bisacetyl deuteroporphyrin dimethyl ester(Ⅳ). The results showed that the yield of hematoporphyrin(Ⅱ) reaches to the highest of 98.5% when the temperature is 35 ℃ and the reaction time is 25 h. The yield of hematoporphyrin dimethyl ester is 72.1% when the catalyst is anhydrous hydrogen chloride. The cost of 3,8-bisacetyl deuteroporphyrin dimethyl ester(Ⅳ) was decreased greatly when the oxidant is Jones reagent. The target products were characterized with 1H NMR, IR and MS.